Halogenated nu-benzanthronepyrazolanthrones



Patented Feb. 23, 1932 UNITED STATES `imi: ALBERT xUNz, or MANNHEIM, ma nur. .toenam LUnmesnAFEu-onrnmnmnn, GERMANY, assmaaons me PATENT oEElcE AND Lemon nEnrnoLnoF GENERAL Nimm WORKS, INC., OF NEW YORK, Y., A CORPORATION OF lDELAWIM f moeizaam n-nnuzanrnnoNEPYnAzoLanmoNns In Drawing. Application `Meld` April 94, 19%,"Serla1` No. 447,110, and tn Germany April 27, 1929.

The present invention relates to thehaloge4 nation of N-benaanthronepyrazolanthrones. We have found that N-,henzanthronepy razolanthrones can be halogenated in a .man-

5A ner easily carried out in practice treating y with an `inorganic halogenating agent in the absence of a diluent. `Halogenating catalysts, in particular non-metallic catalysts, such for example as iodine, sulphur and com- 1|)A pounds thereof, are preerablyadded to the reaction mixture; As halogenating agents the ,free halogens may :be employed as Well-as chlorsulphonic acid, sulphuryl chloride and such fused anhydrous metal fhalides as dissociete at elevated temperatures splitting off halogen, such as for example the halides of aluminum, iron, antimony, n'lezrcuny7 and the like. We Wish ourpa'esent invention .to be midenstood as not comprising the co+employ `:Intent of several of these inorganic `halogenating agemtsand the-appended claims are to abe read with this limitation,` The `process acconding 'to our present invention consists therefore in `treating `the N-benzanthronepyraaolanthrones with fleehalogen at ordinary o1' slightly elevated temperatures, for example by grinding the initial `.material in a stneam `of chlorine or in bromne yor usulphuryl chloride, or heating the 4initial material -with one of the said other inorganic halogenating agents at temperatures at `which they split oil' halogen which in the oase of chlorsulphonic acid is at least about 65 C., the temperature to be used with the `anhydrous ,metal `halides is different `With thesingle metal halides, and is for example at least about 100 `C.,in the case of iron and antimouy chloride, Whereas With aluminum chloride the :temperature should be at least .about 140 C. The melting points of the said metal hfalides may belowered by the addition of suitable substances, tor example the rhali des ofallali and alkaline earth metals. The process according to the ,present invention is particularly suitablefor further halogenating y, Nfbeuzanthronepyra zolanthrones already containing halogen either by introducing further amounts lof the halogen already present or a diiferent halogen. `Moreover7 the Vprocess has the further 50 advantage that the products are obtained in a` y new dyestui's.

` state in which 'they maydirec`t`ly be used for"- dyeing. i Y f lThe dyestulls containing bromine, or bromine and chlorine or iodine, or all three haloo'ens in the molecule `thus obtained y usually `dissolve in concentrated#sulphuric acid giving violet fcolorations,;gi,ve green blue vats and usually ldye `cotton greenish marine blue shades `having excellent properties of fastness. In addition they fare valuable in. tei-mediate products `for the manufacture of YThe corresponding leuco esters or Aleuco preparations may be easily obtained from the dyestuls according to the usual methods. y c5 The crude ldyestui's" may be purified if4 necessary bythe lusualmethods as forexam i le by "crystallization from or boiling upvwith solvents of high boiling point or by crystallization from sulphuric acid by Way of they-` `anonima sulphate or by treatment with oxidizing agents as for example by treatment inthe torna oftheir aqueous `pactes withalkali or alkali-ne earth metal hypochlorites. y l

The following examples Willofurther illus-A trate the natume of `this invention, but the invention is not restrictedito these examples. The parts are by Weight. l

Ewa/infile 1 i 45 parts of N-benzanthronepyrazolanthrone in 450parts of chlorsulphonic acidare heated for several hours at from '60 to 65 C. after lthcaddition `of 10 "partsof iodine." When a sample taken out obviously contains chlorine the whole is allowedto cool, if necessary diluted with concentrated sulphuric acid, poured into Wateryboiled for ashorttime and filtered-by suction while liot. The `dyesull" `obtained which by analysisis adichloro-.N-benzanthonepyrazolanthrone dyes cotton marine blue shades which are more greenish than those of theinitial material anddifers in this respect form all the `chloro `derivatives `,ofthis classici bodies hitherto known, a :difference which maybe attributed ,to the dil'erence in the `position off the chlorine atoms ,in the molecule. The yield ol? the dyestui, `which is Fobtained in a form in which it lis ready for use, is excellent. The reaction product when 100 f shades.

dry is a blue powder which dissolves in con-` centrated sulphuric acid giving a violet coloration and gives a blue vat, and dyeings therefrom have an excellentrtastness to light and weather. i

A chlorobromo derivative givingv stillv more greenish dyeings is obtained by brominating the reaction product, .for example by the addition o'f 20 parts of in chlorsulphonic acid.

- A Example 2 i1200parts of bromine are poured over 445 parts offinely divided N-benzanthrone'pyra- 'zolanthrone, the wholebeing then ground for about 15 hours at between 20 and 30 C. in a ball mill aiter'theraddition 0.1510 parts of iodine. When the desired amount o/,brornine :the addition of iodinev a reaction productis obtained Y dyeing slightly more Vreddish s, v Example .i I 120 parts of sulphuryl chloride are poured Awhile stirring over 44.5 parts of N-benzanthronepyrazolanthrone to which 4 parts of The reaction Imixiodine have been added.

ture is then warmed to between 45 and 50 C. and stirring continued" at the saidV temperature for several hours, whereupon 'the reaction mixture is Worked up in the usual manner. The chloro-'N-benzanthronepyrazolanthrone thus obtained in an excellent yield is a darlrblue powder dissolving in concentrated sulphuricacidgivingV a violet solution and dyeing clear excellently fast navy blue shades fromV a .green blue vat.

Example s 52 parts of monobro'mo-N-bensanthrenepyrazolanthrone obtainable by treating N- benzanthronepyrazolanthrone in oleum of 5v `per cent' strength with the calculatedamount of bromineY are dissolved while stirring in 520 parts of chlorsulphonic acidand heated at be'- tween and 70o afb@ dyeing cotton from a green blue vat 'strong' desired content of chlorine. "lh'e reaction i .mixture is then allowed to cool Vand*worked l up in the usual manner.v

N-benzanthronepyrazolanthronev thus obtained is a violet blue paste and furnishes on .parts Aof selenium untilY a bromine to the solutiony filtered` off, :washed The dibromo-N- .A

"tives which comprises treatinga N-'benzanthronef zanthronepyrazolanthron'es cotton strong clear navy blue shades of lvery good astness from a green blue vat;

Ewample 5 62 parts of dibrorn-N-benzanthronepyrazolanthrone obtainable by brominating N- V'benzanthronepyrazolanthrone in oleum are heated at between and 90 C. in 600 parts of chlorsulphonic acid after the'fadditio'n 'of l 6'parts of iodine until 2 atoms of chlorine have been taken upper each molecule of the initial material; The reaction mixture is then allowed to cool and worked up as usual. The dichlorodibrome-N-benzanthronepyra- Zolanthrone thus obtained in an excellent yield and a state of great purity is a violet bluek paste and av dark blue powder when dried, crystallizes from solvents of high boiling poing such "as-for examplenitrobenzene in violet blue needles, dissolves in anhydrous-ZA sulphuric acid to `give a violet solution and dyes the vegetable fibre from a green blue vat vstrong clear navy blue'shades oi excellent tastness.

l. A process-of producing halogenderivatives of Y -N-benzanthronepyrazolanthrone, which comprises treating .a N-benzanthronelpyrazolanthrone with an inorganic halogenatng agent in the absence of a diluent. I i' f 2. 'process ofproducing halogen derivatives of N-benzanthronepyrazolanthrone, which'cornprises ,treating a N-benzanthronepyrazolanthrone with an inorganic halogen-A I ating agent in the absence of a diluent andv in* the'p'resence of a h'alogenating Catalystfv I" 3. A process of producing halogen derivatives vof y .N-benzanthronepyrazolanthrone, which comprises treating a N-benzanthrone- ,pyrazolanthrone' with chlorsulpho'nic, acid kat atemperature above about 65 C.

M4.' A process oftproducing halogen derivao'f N-benzanthronepyrazolanthrone,

Apyraz'olanthronewith chlorsulphonic acid at a temperature above about'65v" C in the presence of a non-metallic halogenating catalyst. As new articles of manufactureN-bencontaining 'at least two different halogens, dissolving in V concentrated sulphuricacid to give blue red solutio s and dyeing cotton from green blue vats navy yblue shades. i e I A .6.v As a new article of manufacture dichlorodibromo N benzanthronepyrazolanthrone forming a violet blue paste and a dark' blue powder, dissolving in anhydrous sulphuricacid to give a violet solution and clear navy ,blue shades. c

In testimony whereof lwehave hereunto set MAX ALBERT KUNZ KARL KOEBERLE. ERICH BERTI-IOLD.'

iWhat we claim is: i fa" "ico 

